Method of etching an object, method of repairing pattern, nitride pattern and semiconductor device

ABSTRACT

A method of manufacturing a compound layer, containing a nitrified metal as a major component thereof and having a predetermined microstructure pattern, includes: an ion implantation step for implanting hydrogen ions into a predetermined region of a compound layer formed on a substrate to form an implanted region; and an etching step for selectively etching the implanted region by using a gas containing at least oxygen, to remove the implanted region of the compound layer while maintaining the other region as a microstructure pattern. By introducing a halogen element like fluorine in addition to hydrogen, fabrication of the pattern can be executed more reliably and more easily. As a result, volatility of reaction products produced upon etching the compound layer is enhanced, and micro-loading effects are suppressed. Thus, there are provided a method of fabricating a pattern of a compound layer capable of improving the CD controllability without using a dummy pattern, for example, and a compound layer having a microstructure pattern.

BACKGROUND OF THE INVENTION

This invention relates to a method of etching an object, a method ofrepairing a pattern, a nitride pattern and a semiconductor device, andmore particularly to methods for making and repairing a microstructurepattern of a nitride film such as chromium nitride (CrN_(x)) or galliumnitride (GaN) usable for manufacturing semiconductor devices or opticaldevices, and a nitride pattern obtained by any of those methods as wellas a semiconductor device having such a nitride pattern.

The invention is applicable to various fields such as masks suitable foruse in exposure processes using various beams like optical orelectrically charged beams or x-rays, or liquid crystal displays usingthose masks.

A lot of nitrides including metallic nitrides or nitride semiconductorsare materials that contribute to enhancing higher performances andhigher functions of various devices such as electronic devices andoptical devices, for example, importance of process techniques formaking microstructure patterns of various nitrides is progressivelyincreasing. For example, metal material films containing chromium (Cr)as their major components are currently used most in opaque orattenuating phase-shift materials of photomasks (or reticles) forexposure or transference in photolithography. Additionally, since theuse of chromium nitride (CrN_(x)) films facilitates to control the filmstress, they have been proved to be useful also as hard mask materialsfor making absorber patterns for X-ray exposure masks (Japanese PatentLaid-Open Publication No. 11-65095). Then, along withmicrominiaturization of LSI elements and other circuit elements, thereis a strong demand for developments of techniques for makingmicrostructure patterns of exposure mask material films, especiallythose containing chromium as their major component.

In the field of lithography, for the purpose of transference orresolution of patterns smaller than exposure wavelengths, the use ofoptical proximity repair (OPC) masks and phase shift masks isindispensable for accurately controlling complicated geometry of maskpatterns and pattern sizes.

With reduced pattern size of films made of those materials containingchromium as their major component, dry etching using chlorine (Cl₂) iscurrently used in lieu of conventional wet etching. In the process ofmaking microstructure patterns by dry etching, there is the problem that“micro-loading effect” occurs due to a difference in pattern density anddegrades the uniformity of pattern sizes. The “micro-loading effect”pertains to a phenomenon occurring upon simultaneously etching a patternof a higher density and a pattern of a lower density: due to adifference in etching rate of a film from a location to another, theamount of reaction products by etching becomes locally dense or sparce,and convection of a large amount of reaction products by etching with alow volatility causes an un-uniformity in etching rate. Therefore, inthe process of manufacturing photomasks or semiconductor integratedcircuits, efforts are made toward suppressing the micro-loading effectby placing a dummy pattern in a region having no circuit pattern to bemade.

On the other hand, not only microprocessing techniques, but also defectinspection/repair are needed for advanced photolithography. In case offine, complex features, inspection and repair of defects especially inOPC masks and various types of phase shift masks are not limited to theinspection and repair pinholes or particles, for example, but includeinspection and repair of defects of transparency of films, phase shiftdifference, or the like, in addition of defects of micro OPC patterns,foreign matters, image placement error of patterns and CD deviation ofsizes, establishment of techniques for accurate inspection and repairfor that purpose is longed for.

Currently employed defect repair techniques include those using a laserand those using a focused ion beam, and the latter is used morecommonly. A repair technique using a focused ion beam is configured toremove “opaque defects” like bridges by irradiating them with a galliumion (Ga⁺) beam while blowing an etching gas, if necessary, and correct“clear defects” like pinholes by irradiating them with a gallium ion(Ga⁺) beam while blowing a carbon-hydrogen gas to make a carbon compoundcoating.

Pattering of nitride semiconductor with fine features has becomeessential for the fabrication of more advanced devices of various types.For example, light emitting diodes using III-V nitride semiconductorssuch as GaN, AlN, InGaN, and so on, are being brought into practical useas light sources over a wavelength range from ultraviolet to green.Additionally, researches and developments are progressing toward theiruse as electronic devices using their properties as wide gapsemiconductors. Then for higher performance of those devices, trials arebeing made for making fine patterns of various nitride semiconductors.Heretofore, however, plasma etching techniques using the etching gas,containing Cl₂ (chlorine) or F₂ (fluorine) gases have been used inetching processes, and these techniques involve the problems thathigh-density plasma damages surfaces of devices and changes incomposition ratio of Ga/N, etc. on surfaces.

Reaction products by etching of chromium (Cr)-group materials areusually low in volatility and are liable to cause the micro-loadingeffect in dry etching. Therefore, it is an important issue how CD(critical dimension) controllability is enhanced in photomasks orreticles or in other circuit substrates.

Especially regarding a photomasks having an OPC pattern, since thepattern size of an OPC pattern is smaller than that of other patterns,and highly anisotropic etching is required there. Although the biasvoltage to the substrate and the vapor pressure of the etchant gas, thereaction products are driven to adhere the side-walls of patterns byhigh pressure of the etchant gas and this adhesion of reaction productsprevents from the etchant adhering to the etching material. As a result,the micro-loading effects is liable to occur, and it is extremelydifficult for the mask to be CD controlled in the reticle plane. If theCD controllability is poor, the resultant pattern size of the reticlewill be un-uniform between its central portion and its peripheralportion.

Conventionally proposed techniques with a dummy pattern requiresimulation calculation for optimizing the pattern configuration anddensities using dummy patterns, and it is difficult to simplify amanufacturing process or make it inexpensive by using such techniquesfor the mask with OPC patterns.

Dry etching using a chlorine-group gas involves another problem causedby toxicity of the chlorine gas to human bodies and its highcorrosiveness, for which there is the need for nitrogen purge of thechambers and pipes after etching and the need for extreme attention inhandling it.

Furthermore, in case of repairing defects of photomasks, reticles orvarious kinds of circuit substrates using chromium-based films, opaquedefect repair by a focused ion beam or a laser beam may excessivelyremove irradiated portions of substrates other than the defects, or mayresult in deterioration of transmittance by the implanted gallium ions,and damages to transparent substrates were a serious problem.

Similarly to etching of chromium-based materials, also in fabrication ofpatterns of various kinds of metallic nitrides and nitridesemiconductors or other materials containing nitrogen, the micro-loadingeffect and defects of patterns occur in the etching process, andsuppression and repair of them are serious issues when fabricatingdevices.

SUMMARY OF THE INVENTION

Under acknowledgement of those problems, it is an object of theinvention to provide a method of etching an object, a method ofrepairing a pattern, a nitride pattern and a semiconductor device thatsuppress or minimize the micro-loading effect as a result of etching ofa nitride material with increasing the volatility of reaction productsand can ensure CD controllability without using a dummy pattern, orother like means.

According to the invention, there is provided a method of etching anobject comprising: preparing the object containing nitrogen; implantinghydrogen into a predetermined region of the object; and selectivelyremoving the predetermined region from the object, by exposing theobject to an atmosphere containing excited oxygen.

According to the invention, there is also provided a method of repairinga pattern comprising: making a portion of the pattern to be removedcontain nitrogen and hydrogen; and etching the portion to be removed byexposing to an atmosphere containing excited oxygen.

According to the invention, there is also provided a nitride pattern,comprising a nitride layer having a selectively removed portion, theportion being implanted with hydrogen and then exposed to an atmospherecontaining excited oxygen so as to be selectively removed the portionfrom the nitride layer.

According to the invention, there is provided a semiconductor devicecomprising: a substrate; a semiconductor element formed on thesubstrate; a nitride layer formed over the semiconductor element, thenitride layer having a selectively removed region, the region beingimplanted by hydrogen and then exposed to an atmosphere containingexcited oxygen so as to be selectively removed the region from thenitride layer.

According to the invention, there is also provided a semiconductordevice comprising: a substrate; a plurality of transistor elementsformed on the substrate; an interconnect layer formed over thetransistor elements; a first nitride layer below the interconnect layerhaving a first air portions; a second nitride layer on the interconnectlayer having a second air portions; and a protective layer over thesecond nitride layer.

According to the invention, there is also provided a method ofmanufacturing the semiconductor device having a substrate, a pluralityof transistor elements formed on the substrate, an interconnect layerformed over the transistor elements, a first nitride layer below theinterconnect layer having a first air portions, a second nitride layeron the interconnect layer having a second air portions, and a protectivelayer over the second nitride layer,

the method comprising: forming the first nitride layer without the firstair portions and the second nitride layer without the second airportions; implanting hydrogen into corresponding portions of the nitridelayers, the corresponding portions being the first and the second airportions to be made; and irradiating plasma containing excited oxygen tothe nitride layers to remove the corresponding portions thereby makingthe first and the second air portions in the nitride layers.

Especially when a nitride semiconductor is used as the compound layer,it can be used for patterning of an electronic device or light emittingelement that emits light in a short wavelength range of ultraviolet orblue, for example. In the specification, “nitride semiconductors” meanany III-V compound semiconductors expressed by the general formulaB_(x)In_(y)Al_(z)Ga_((1-x-y-z)) N(0≦x≦1, 0≦y≦1, 0<z1).

As summarized above, according to the invention, when the etching methodby oxygen plasma using effects of H⁺ ions for etching a thin film havingas its major component a nitrogen-containing compound layer of a metalsuch as chromium or nitrogen-containing compound semiconductor, etchingtakes place by chemical etching that produces highly volatile reactionproducts. Therefore, unlike the conventional etching methods usingchlorine-group gases, the invention can suppress the micro-loadingeffect and can fabricate precise OPC (optical proximity repair) masks,Levenson phase shift masks, or and so on.

Additionally, according to the invention, a gas containing hydrogen andan oxygen gas can be used for etching instead of chloride gasesheretofore used by the conventional dry etching methods, so it is amicrostructure pattern fabrication method that is simple and safe.

Further, according to the invention, when repairing defects ofphotomasks, reticles or various kinds of circuit substrates usingchromium or its compound layers, accurate repair is possible withoutdamaging portions other than defects of patterns.

Furthermore, according to the invention, by implanting a halogen elementsuch as fluorine in addition to hydrogen, patterns can be made morereliably, more easily.

Moreover, according to the invention, it is possible to manufactureexposure masks and various kinds of microstructure patterns ofnitrogen-containing compound layers simply and inexpensively. At thesame time, by using the inexpensive exposure masks, the cost oflithography process can be reduced, and inexpensive semiconductordevices or optical elements can be supplied. Thus the invention has alot of industrial advantages.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will be understood more fully from the detaileddescription given herebelow and from the accompanying drawings of thepreferred embodiments of the invention. However, the drawings are notintended to imply limitation of the invention to a specific embodiment,but are for explanation and understanding only.

In the drawings:

FIGS. 1A through 1D are cross-sectional views that show the basicconcept of a process according to an embodiment of the invention;

FIGS. 2A through 2I are cross-sectional views that show a manufacturingprocess, taken as the second example according to the same embodiment;

FIGS. 3A through 3E are cross-sectional views that show a process ofmanufacturing a microstructure pattern, taken as the third exampleaccording to the same embodiment;

FIGS. 4A through 4C show enlarged images of a superfine pattern obtainedby the third example, which were observed through a scanning electronmicroscope;

FIGS. 5A through 5C are diagrams that show the concept of a method ofrepairing defects in a photomask containing Cr as a opaque filmmaterial;

FIGS. 6A through 6C are diagram that show the concept of a method ofrepairing defects in a photomask containing CrN_(x) as a opaque filmmaterial;

FIG. 7 is a diagram that shows the concept of a defect repairing devicefor executing a defect repairing method, taken as the fourth exampleaccording to the same embodiment;

FIG. 8 is a flow chart that shows a process flow for the defectrepairing device according to the same embodiment;

FIG. 9 is a flow chart that shows a manufacturing process of asemiconductor device;

FIGS. 10A through 10D are cross-sectional views that show the concept ofa process according to the second embodiment of the invention;

FIGS. 11A through 11F are cross-sectional views that roughly show acentral portion of a process of making a CrN microstructure pattern,used in the sixth example of the invention;

FIGS. 12A through 12D are enlarged images of patterns obtained by theprocess A and the process B in the sixth example, which were observedthrough a scanning electron microscope;

FIGS. 13A through 13D are cross-sectional views that roughly show acentral portion of a process of making a TiN microstructure pattern usedin the sixth example of the invention;

FIGS. 14A through 14C are graphs that show results of XPS analysis,which were obtained in the sixth example of the invention;

FIGS. 15A through 15C are diagrams that show the concept of a method ofrepairing defects in a photomask according to the seventh example of theinvention;

FIGS. 16A through 16C are diagrams that show the concept of a method ofrepairing defects in a CrN photomask according to the second embodimentof the invention;

FIG. 17 is a flow chart that shows the flow of the defect repairingmethod by the second example of the invention;

FIGS. 18A through 18D are cross-sectional views that roughly show acentral portion of a process, taken as the eighth example of theinvention;

FIG. 19 is a diagram that shows the concept of a semiconductor devicemade by the invention;

FIGS. 20A through 20G are cross-sectional views that roughly illustratecentral steps of the instant example; and

FIG. 21 is a graph showing the relationships between the accelerationvoltage of the hydrogen implantation and the depth of thehydrogen-implanted region.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Now referring to the drawings, embodiments of methods of making apattern and patterns of compounds according to the invention areexplained in detail.

(First Embodiment)

FIGS. 1A through 1D are cross-sectional views that show the basicconcept of a process according to the first embodiment of the invention.

In this embodiment, a compound layer 1 containing nitrogen is firstformed on a substrate 2 as shown in FIG. 1A.

Next as shown in FIG. 1B, a resist mask 3 of a predetermined pattern isformed on the compound layer 1. Chromium nitride, for example, can beused as the material of the compound layer 1.

Next as shown in FIG. 1C, hydrogen ions 4 are implanted. Then, in thisprocess, the intrusion of hydrogen ions 4 is blocked by the mask 3, andthe hydrogen ions are selectively implanted only into portions of thecompound layer 1 exposed through apertures of the mask 3 to formhydrogen-implantation regions 1A there.

Then as shown in FIG. 1D, a gas 5 containing excited oxygen, such asoxygen plasma, is exposed. As a result, the resist mask 3 is removed,and those portions of the compound layer 11 implanted with hydrogen ions4 are etched and removed. The reason why the compound layer 1 is etchedprobably lies in that highly volatile reaction products with anextremely high equilibrium vapor pressure are caused by reaction of thehydrogen-containing compound layer 1 with oxygen.

As explained above, this embodiment uses quite a unique phenomenon thata hydrogen-implanted compound layer is etched when exposed to anatmosphere of excited oxygen. Then, the invention gives the followingeffects.

First, according to the invention, the etching caused by excited oxygenin the compound layer implanted with H⁺ (hydrogen) ions is chemicaletching with very volatile reaction products. Therefore, as comparedwith the existing etching technique using a chloride gas, micro-loadingeffect can be suppressed, and CD controllability on the substrate can beenhanced. As a result, optical proximity repair masks, Levenson phaseshift masks, and so on, having a high accuracy can be fabricated easilyand reliably.

Additionally, the microstructure pattern fabricating method according tothe embodiment enables simple and safe etching only with ahydrogen-containing gas and an oxygen gas instead of a chlorine compoundgas heretofore used in dry etching of a material film containingchromium as its major component. Further, according to the invention,also when defects in photomasks, reticles and various kinds of circuitboards using chromium compound films should be repaired, they can bemodified accurately without damaging the remainder portions.

It is also possible to fabricate chromium-based exposure masks andvarious kinds of microstructure patterns easily and inexpensively.

Moreover, through trial manufacture and researches, the Inventorrecognizes that metallic nitrides usable in the embodiment are notlimited o chromium nitrides, but the invention is similarly applicableto other nitrides of titanium (Ti), aluminum (Al), molybdenum (Mo),tungsten (W), gallium (Ga), indium (In) and boron (B).

The first embodiment will be explained below in greater detail withreference to the first to fifth examples of the invention.

(First Example)

A photomask fabricating method using a chromium nitride (CrN_(x)), takenas the first example of the invention, is first explained with referenceto FIGS. 1A through 1D.

First referring to FIG. 1A, a chromium nitride film 1 was deposited on asubstrate 2. More specifically, by introducing a cleaned 6.35 mm thick6-inch quartz substrate 2 into a reactive sputtering apparatus, using Cras the target material, the CrN_(x) film 1 with 10 nm thickness as aopaque film, was deposited, using a mixed gas of a nitrogen/argon mixedgas under the pressure of 5 mTorr. After that, through ultrasoniccleaning, a mask blanks were obtained.

In case that a CrON film (not shown) as an anti-reflection film is to beformed on the CrN_(x) film, the film is deposited in the same chamber,using a mixed gas of nitrous oxide (N₂O) and argon under to pressure of5 mTorr such that the total thickness with the CrN_(x) film 1 becomes100 nm. Thereafter, through ultrasonic cleaning, a mask blanks areobtained.

Next as shown in FIG. 1B, a resist mask 3 is formed. More specifically,ZEP7000B (Nippon Zeon), commercially available electron beam resist, wascoated on the surface of the mask blanks with a spin coater at the spinvelocity of 1800 rpm for 50 seconds. Then through a baking process usinga hot plate, a 500 nm thick photosensitive film was made, and a patternwas written by using an electron beam writing apparatus having theacceleration voltage of 75 kV. For the purpose of obtaining a desiredwriting accuracy, multiple exposure method for forming a pattern byfour-pass writing was employed, and optical proximity effect repair wasexecuted by repairing the amount of irradiation. After the writing, theresist mask 3 was developed.

After that, as shown in FIG. 1C, hydrogen was implanted. Morespecifically, hydrogen plasma 4 of a mixed gas of hydrogen and nitrogen(gas pressure: 0.5 Pa, flow rate: 100 sccm) was irradiated for threeminutes in a plasma etching apparatus under the antenna output of 750 Wand the bias output of 300 W. When the hydrogen plasma is irradiated onthe substrate, most of H⁺ ions with small mass intrude deeply into theCrN_(x) and CrON films under the openings of the resist mask, whereasthe resist could prevent the H+ ions from penetrating the CrN_(x) andCrON films. This was confirmed by secondary ion mass spectrometry(SIMS).

Next as shown in FIG. 1D, the structure is exposed to a oxygen plasma.More specifically, the resist mask 3 was removed by oxygen plasma 5 withthe antenna output of 500 W (gas pressure: 0.7 Pa, flow rate: 100 sccm),and the hydrogen plasma-irradiated CrN_(x) film 1 was etched by theoxygen plasma. Thus the pattern was obtained.

(Second Example)

Next explained is the second embodiment of the invention.

FIGS. 2A through 2I are cross-sectional views that show a manufacturingprocess according to the same embodiment. That is, these figuresillustrate a manufacturing process for fabricating a single trench typeLevenson phase shift mask according to the same.

First as shown in FIG. 2A, a chromium nitride layer 1 and a siliconoxide film 6 were deposited on a substrate 2. More specifically, byintroducing a cleaned 6.35 mm thick 6-inch quartz substrate 2 into areactive sputtering apparatus, using Cr as the target material, theCrN_(x) film 1, 100 nm thick and functioning as a opaque film, wasdeposited, using an argon gas under the pressure of 5 mTorr. After that,through ultrasonic cleaning, a mask blanks were obtained. In case that aCrON film (not shown) as an anti-reflection film is to be formed on theCrN_(x) film, the film is deposited in the same chamber, using a mixedgas of nitrous oxide (N₂O) and argon under to pressure of 5 mTorr suchthat the total thickness with the CrN_(x) film 1 becomes 100 nm. Afterthat, a 100 nm thick SiO₂ film 6 was deposited on the mask blanks in thesame reactive sputtering apparatus, changing the target and the gas.

Next as shown in FIG. 2B, a first resist mask 3A was formed. Morespecifically, ZEP520 (Nippon Zeon), commercially available electron beamresist, was coated with a spin coater at the spin velocity of 1500 rpmfor 50 seconds. Then through baking process using a hot plate, a 500 nmthick resist layer was formed, and a pattern was written by using anelectron beam writing apparatus having the acceleration voltage of 75kV. For the purpose of obtaining a desired accuracy, multiple exposuremethod for forming a pattern by four-pass exposure was employed, andoptical proximity effect repair was executed by repairing the amount ofirradiation. After the writing, the resist mask 3A was developed.

After that, as shown in FIG. 2C, hydrogen was implanted. Morespecifically, hydrogen plasma 4 of a mixed gas of hydrogen and nitrogen(gas pressure: 0.5 Pa, flow rate: 100 sccm) was irradiated for threeminutes in a plasma etching apparatus under the antenna output of 750 Wand the bias output of 300 W. Thereby, hydrogen-implanted regions 1Awere formed to lie under openings of the resist mask 3A.

Next as shown in FIG. 2D, the resist mask 3A and the SiO₂ film 6 wereremoved. More specifically, they were removed by using a spin coater,coating o-dichlorobenzene and ammonium fluoride liquid, respectively andconducting wet etching.

Next as shown in FIG. 2E, a second resist mask 3B was formed. Morespecifically, after cleaning the surface of the mask blanks, by againusing the spin coater, a 500 nm thick photosensitive resist film 3 wasformed by coating ZEP-7000B (Nippon Zeon), commercially availableelectron beam resist, and thereafter baking it with a hot plate. Then apattern was written by using an electron beam writing apparatus havingthe acceleration voltage of 75 kV. For the purpose of obtaining adesired writing accuracy, multiple exposure method for forming a patternby four-pass writing was employed, and optical proximity effect repairwas executed by repairing the amount of irradiation. After the writing,the resist was developed, and resist mask 3B was formed.

The image placement accuracy of the pattern written in this processrelative to that written in the step shown in FIG. 2B was 20 through 30nm at 3σ-level.

Thereafter, as shown in FIG. 2F, the structure was exposed to plasma 5Aof a mixed gas of sulfer hexafluoride (SF₆) and oxygen.

As a result, as shown in FIG. 2G, the hydrogen-implanted regions 1A ofthe CrN_(x) film under openings of the resist mask 3B were etched andremoved, and the quartz substrate 2 was also etched. The quartzsubstrate 2 was etched only to a predetermined depth 7 (thickness withwhich the phase shift of the quartz by exposure light became π radian).

Next as shown in FIG. 2H, the structure was exposed to oxygen plasma 5B.That is, as a result of exposure to oxygen plasma 5B of the antennaoutput of 500 W (gas pressure: 0.7 Pa, flow rate: 100 sccm), the resistmask 3B was removed, the hydrogen-implanted region 1A of the CrN_(x)film was etched, and as shown in FIG. 2I, a single-trench Levenson phaseshift mask 10 was fabricated.

(Third Example)

Next explained is the third example, which is an example of making asuper-fine structure with a pattern size of 10 nm or less.

FIGS. 3A through 3E are cross-sectional views that show a manufacturingprocess according to the same embodiment.

First as show in FIG. 3A, a chromium nitride layer 1 and a silicon oxidefilm 6 were deposited on a substrate 2. More specifically, byintroducing a cleaned 0.7 mm thick 8-inch Si substrate 2 into a reactivesputtering apparatus, using chromium as the target material, the CrN_(x)film 1 with 100 nm thickness as a opaque film, was deposited, using amixed gas of nitrogen and argon under the pressure of 5 mTorr.Additionally, a 500 nm thick SiO₂ film 6 was deposited by changing thetarget and the gas.

Next as shown in FIG. 3B, a resist mask 3 was formed. More specifically,ZEP520 (Nippon Zeon), commercially available electron beam resist, wascoated with a spin coater at the spin velocity of 2000 rpm for 50seconds. Then through baking process using a hot plate, a 350 nm thickphotosensitive layer was made, and a pattern was written by using anelectron beam writing apparatus having the acceleration voltage of 75kV. For the purpose of obtaining a desired writing accuracy, multipleexposure method for forming a pattern by four-pass writing was employed,and optical proximity effect repair was executed by repairing the amountof irradiation. After the writing, through development, the resist mask3 was made.

After that, as shown in FIG. 3C, etching and hydrogen-implantation wereconducted. More specifically, the plasma 4 of a CHF₃ gas (gas pressure:0.6 Pa, flow rate: 100 sccm) was irradiated for three minutes in aplasma etching apparatus under the antenna output of 750 W and the biasoutput of 300 W. As a result, selective portions of the silicon oxidefilm 6, which were not covered by the resist mask 3, were etched, andhydrogen-implanted regions 1A were formed at exposed portions of theCrN_(x) film 1.

Next as shown in FIG. 3D, the fine structure was fabricated by oxygenplasma. More specifically, as a result of irradiation of oxygen plasma 5with the antenna output of 500 W (gas pressure: 0.7 Pa, flow rate: 100sccm) for 15 minutes, the resist mask 3 was removed, and thehydrogen-implanted regions 1A of the CrN_(x) film were etched andremoved.

Further, oxygen plasma 5 with the antenna output of 500 W (gas pressure:0.7 Pa, flow rate: 100 sccm) was continuously irradiated. Thereby, theCrN_(x) film 1 left under the SiO₂ film 6 was side-etched, and it wasconfirmed that microstructure patterns with a size of 10 nm or lesscould be made as well.

FIGS. 4A through 4C are enlarged diagrams of images of a super-finepattern obtained by the same example, which were observed through ascanning electron microscope. As shown in these diagrams, in anyportions of the CrN_(x) film 1 where oxygen gas could touch, all groovesincluding extremely fine grooves, were side-etched. That is, it isindicated that, according to the embodiment, reaction products resultingfrom chemical etching of metallic nitride films by oxygen are highlyvolatile.

The reason why the CrN_(x) film located under the resist mask 3 was sideetched is considered to lie in that part of the implanted hydrogen ionsspread in the CrN_(x) film over the peripheral region underlying aroundthe opening of the resist mask 3 and the SiO₂ film 6 in the step shownin FIG. 3C. While the etching rate by oxygen plasma for CrN filmunderlying the openings of the resist mask 3 was 7.5 nm/minute, theetching rate of the CrN_(x) film under the resist mask 3 was 2.9nm/minute. This difference in etching rate is considered to reflect thedifference in amount of contained hydrogen. By increasing theirradiation time of hydrogen plasma, side etching can be promoted evenunder the SiO₂ film 6.

In order to prevent the CrN_(x) film 1 located under the resist mask 3from being etched by oxygen, the spreading of the hydrogen ion may bereduced. That is, the condition of the implantation may be controlled sothat the straightforward implantation of hydrogen ions could beobtained. Alternatively, the antenna output of oxygen plasma may bedecreased to lower the etching rate. By restricting etching by any ofthese methods, a structure free from side etching as shown in FIG. 3Dcan be fabricated.

The microstructure pattern of the CrN_(x) film according to the examplewas analyzed by X-ray photoelectron spectroscopy (XPS), secondary ionmass spectrometry (SIMS), X-ray diffraction (XRD) and transmissionelectron microscopy. As a result, even after various kinds of plasmaprocessing using hydrogen-containing gas and oxygen gas, no change wasobserved in composition profile of constituent elements other thanhydrogen and in crystalline structure in the CrN_(x) film 1, and it wasconfirmed that damages by irradiation such as defects or dislocation wasnot induced. That is, it was confirmed that no change was brought aboutin optical property, electric property or mechanical property incompound layers used as masks.

Furthermore, for the purpose of reviewing the effects of implantation ofhydrogen ions into the CrN_(x) film 1 employed in the embodiment, thefollowing five samples (A) through (E) were processed with oxygen plasmaof the antenna output of 500 W (gas pressure: 0.7 Pa, flow rate: 100sccm). Results of comparison of etching rates of CrN_(x) films and Crfilms are shown in Table 1.

A) CrN_(x) film prepared by irradiating plasma of CHF₃ gas of theantenna output of 750 W and the bias output of 300 W (gas pressure: 0.6Pa, flow rate: 100 sccm) on the surface of CrN_(x) film for 30 seconds;

B) CrN_(x) film prepared by irradiating plasma of SF₆ gas of the antennaoutput of 750 W and the bias output of 300 W (gas pressure: 0.6 Pa, flowrate: 100 sccm) on the surface of CrN film for 30 seconds;

C) Cr film prepared by irradiating plasma of CHF₃ gas of the antennaoutput of 750 W and the bias output of 300 W (gas pressure: 0.6 Pa, flowrate: 100 sccm) on the surface of Cr film for 30 seconds;

D) CrN_(x) film prepared without plasma processing; and

E) Cr film prepared without plasma processing.

TABLE 1 Etching rate by oxygen plasma A) CrN (CHF₃-30s) 7.4 nm/min. B)CrN (SF₆-30s) 1.0 nm/min. C) Cr (CHF₃-30s) 0.3 nm/min. D) CrN (bulk) 1.1nm/min. E) Cr (bulk) 0.2 nm/min.

By comparing etching rates of samples A and B, the effect ofhydrogen-containing gas is confirmed. Further, by comparing etchingrates of samples A and C, a difference is observed between the CrN_(x)film and the Cr film, and it is appreciated that selective etching ofthe CrN_(x) film and the Cr film is possible.

As explained above, it is appreciated that a photomask with a desiredhigh accuracy can be fabricated by dry etching using the hydrogen ionimplantation effects of the CrN_(x) film.

The mask fabricated by the embodiment has the following advantages.

First, when the CrN_(x) film containing Cr as its major component isetched by the etching method by oxygen plasma to use the H⁺ ion effect,since the CrN_(x) film is etched by chemical etching with highlyvolatile reactive products, the micro-loading effect is suppressed ascompared with the existing conventional etching method using chlorinecompound gas, and enhancement of CD controllability can be expected.

In case of photomasks for optical lithography, with reduced patternsize, it is necessary to make a much smaller opaque pattern like serifsand jogs for optical proximity repair, or make a phase shift mask,particularly such as Levenson phase shift mask. Since the aspect ratioof the opaque pattern is high, it is difficult to control the size, theshape and the CD uniformity of patterns with a high accuracy when usingconventional methods using wet etching or dry etching in themanufacturing process. However, by making a photomask by the etchingmethod according to the example, it is possible to easily make amicrostructure pattern with high accuracy inexpensively and to fabricatea high-performance phase shift mask.

Second, hydrogen-containing gas and oxygen gas can be used for etchingin lieu of chlorine compound gas heretofore in existing conventional dryetching methods of films containing Cr as their major component.Therefore, the method according to the example is advantageous inenabling easy and safe fabrication of a microsturcture pattern.

Although the foregoing example has been explained as using sputteringfor deposition of the film, it is also possible to use CVD (chemicalvapor deposition), or the like.

Furthermore, gases containing hydrogen other than CHF₃, CF_(x)+H₂ andNH₃ indicated above are also usable in the plasma processing using ahydrogen-containing gas. Moreover, it is possible to control the etchingrate and pattern configuration of the CrN_(x) film by hydrogen plasma bychanging the antenna output and the bias output. Similarly,configuration after etching can be also changed by changing the antennaoutput or applying a bias upon irradiation of oxygen plasma.

Further, etching rate and configuration of the CrN_(x) film can bechanged also by adding a gas like N₂, Cl₂, H₂ or the like, in additionto oxygen, in the oxygen plasma processing.

Additionally, in the explanation made above, although the compound hasbeen written as CrN_(x), the composition ratio x representing itscomposition is not limited to 1, the embodiment is similarly applicableto chromium nitride films of other composition ratios. Furthermore, theembodiment is similarly applicable also to various kinds of nitridessuch as CrCN and CrCON, for example, as compounds containing chromium(Cr) and nitrogen (N).

Furthermore, the silicon oxide (SiO₂) film 6 used in the instant exampleto fabricate the Levenson phase shift mask may be replaced with anotherfilm that transmits hydrogen ions and is more preferably made of amaterial easy to remove.

(Fourth Example)

Next explained is the fourth example of the invention, which is a methodof repairing defects in a photomask using a chromium compound layer.

First explained is a method of repairing defects in a photomask made ofchromium, with reference to FIGS. 5A through 5C.

FIG. 5A is a diagram that shows a opaque defect 9A has been made of aresidue of a chromium (Cr) film in a part of a photomask pattern 8A ofchromium (Cr) in its fabricating process.

A nitrogen and hydrogen ion beam of 60 kev is irradiated onto the opaquedefect 9A by ion implantation to nitrify chromium (Cr) at the defectportion, and hydrogen is introduced additionally.

As a result, as shown in FIG. 5B, a CrN_(x) region 10 plenty ofimplanted hydrogen ions is formed.

After that, a plasma of oxygen and SF₆ of antenna output of 500 W (gaspressure: 0.7 Pa, flow rate: 100 sccm) is irradiated. As a result, theonly portion of CrN_(x) film forming the opaque defect 9A is selectivelyetched, and the opaque defect 9A is removed and repaired as shown inFIG. 5C.

In this way, defects of the photomask made of chromium (Cr) can berepaired.

Next explained is a method of repairing defects in a photomask usingCrN_(x) as the material of a opaque film, with reference to FIGS. 6Athrough 6C.

FIG. 6A is a diagram that shows a opaque defect 9B has been made of aresidue of a chromium (Cr) film in a part of a photomask pattern 8B ofchromium nitride (CrN_(x)) in its fabricating process.

A hydrogen focused ion beam of 60 keV is irradiated on the opaque defect9B on photomask by ion implantation to form a hydrogen implanted region11 as shown in FIG. 6B.

Then plasma of oxygen and SF₆ of antenna output of 500 W (gas pressure:0.7 Pa, flow rate: 100 sccm) is exposed on photomask. As a result, theonly portion of the CrN_(x) film forming the opaque defect 9B isselectively etched, and the opaque defect 9B is removed and repaired.

According to the method explained above, upon repairing defects in aphotomask, reticle using a chromium (Cr)-based film or in various kindsof circuit boards, high-accuracy repair is ensured without damagingportions other than the defects.

This example for repairing defects in a pattern also utilizes that theetching rate of the CrN_(x) film implanted with hydrogen ions by oxygenplasma is much higher than that of the CrNx film with no hydrogen ionimplantation. Further, also in the defect repair according to theinstant example, even after various kinds of plasma processing usinghydrogen-containing gas and oxygen gas, no change was observed incomposition profile of constituent elements other than hydrogen and incrystalline structure in the chromium (Cr) film or CrN_(x) film, and itwas confirmed by X-ray photoelectron spectroscopy (XPS), secondary ionmass spectrometry (SIMS), X-ray diffraction (XRD) and transmissionelectron microscopy that damages by irradiation such as defects ordislocation was not induced and that no change was brought about inoptical property, electric property or mechanical property in compoundlayers used as masks.

FIG. 7 is a diagram that shows the concept of a defect repairing devicefor executing a defect repairing method according to the instantexample. That is, the device 100 may be made up of a focused ion beamirradiation chamber 110, oxygen-containing plasma irradiation chamber120, and an preparation chamber 130.

The focused ion beam irradiation chamber 110 is for irradiating ahydrogen-containing ions beam focused onto the target, and it canirradiate a nitrogen-containing ions focused beam, when necessary.

The oxygen plasma irradiation chamber 120 is for irradiatingoxygen-containing plasma onto the substrate. It is preferable to use amixed gas including oxygen and halogen gas as the source of the plasma.

The preparation chamber 130 has the function of loading/unloadingphotomasks packed in a cassette, or the like, to be processed andloading/unloading them to or from respective operations chambers.

These chambers are connected and each can be shut by gate valves GV.

FIG. 8 is a flow chart that shows a process flow for the defectrepairing device.

In step S1, the focused ion beam irradiation chamber 110 is adjusted.More specifically, the probe current, optical axis and focus of the ionbeam, and so on, are adjusted.

In step S2, each of photomasks packed in a cassette to be processed istransported from the preparation chamber 130 into the focused ion beamirradiation chamber 110, set and positionally adjusted on a stage.

In step S3, the actual circuit pattern is compared and tested with CADdata which is the data on the design of the mask pattern circuit, andinformation about opaque defects is read out.

Based on the opaque defect information obtained in step S3, an ion beamis irradiated onto defects in step S4. After that, the subject isunloaded from the operation chamber 110 to the preparation chamber 130in step S5.

In step S6, the subject is loaded from the preparation chamber 130 intothe oxygen plasma irradiation chamber 120 and set therein, and oxygenplasma is irradiated onto it in step S7.

After that, in step S8, the subject is unloaded from the operationchamber 120 to the preparation chamber 130.

The flow next returns to step S2 to again load the subject into thefocused ion beam irradiation chamber 110, and in step S3, the actualcircuit pattern is again compared with CAD data of the designed maskpattern circuit to read out opaque defect information from it.

If opaque defects are already repaired, the flow moves to step S9, toexecute inspection and repair of clear defects. After repair of cleardefects, the subject is unloaded from the operation chamber 110 to thepreparation chamber 130 in step S10, and then extracted from thepreparation chamber 130 in step S11. Thus a series of repair process iscompleted.

Regarding repair of clear defects, they can be repaired by locallyirradiating a focused ion beam of hydrogen while blowing an organic gasonly onto the defects and depositing a carbon film on the clear defectsin the focused ion beam irradiation chamber 110 of the same device 100,similarly to the case of opaque defects. Through these steps, photomasksfree from defects can be shipped.

The method of repairing defects according to the embodiment have beenconfirmed to have the following two advantages.

One of the advantages is to ensure high-accuracy repair without damagingportions other than defects of the pattern. Unlike the existing methodof removing defects by sputtering using irradiation of a focused Ga⁺ ionbeam, the embodiment does not damage the base substrate.

In the repair method using an ion beam according to the embodiment, therepair accuracy is determined by scattering of the beam and spreading ofsecondary electrons. However, in case of an ion beam, energy of thesecondary electrons does not affect the accuracy largely. Therefore, incase of light element ions like hydrogen ions, the repair accuracy isdetermined by their dispersion in the film, hydrogen ions do notdisperse widely at the high energy of 60 keV, and back scattering fromthe base substrate of the pattern can be disregarded. Therefore, theextension of their diversion is only about 10 to 20 nm. The repairmethod using a hydrogen ion beam for the hydrogen ion implantationeffect of the CrN_(x) film and a high repair accuracy, ensures highlyaccurate repair for Cr-based photomasks.

The other of the advantages is to ensure easy and inexpensive repair ofdefects on photomasks and various kinds of microstructure patterns.

Although the instant example has been explained as using ionimplantation in the process of nitrifying the Cr film, it is alsopossible to use a laser doping method by focusing laser light in anatmosphere of a nitrogen-containing gas, such as ammonium, for example.In this case, a KrF, ArF or F₂ excimer laser is preferably used, whichcan focus light into smaller area with a high output power forhigh-concentrated implantation.

In the explanation of the instant example, irradiation of a hydrogen ionbeam has been explained only as means for repair of defects in theCrN_(x) film. However, needless to say, it is also possible to use ahydrogen ion beam to fabricate a microstructure pattern of the CrN_(x)film. Additionally, in the explanation made above, although the compoundhas been written as CrN_(x), the composition ratio x representing itscomposition is not limited to 1, the embodiment is similarly effectiveto chromium nitride films of other composition ratios. Furthermore, theembodiment is similarly effective also to various kinds of nitrides suchas CrCN and CrCON, for example, as compounds containing chromium (Cr)and nitrogen (N).

(Fifth Example)

Next explained is the fifth example of the invention, which is a methodof fabricating a micro device using an exposure mask fabricated andrepaired by the first to fourth examples. The “microstructure device”herein pertains to any of semiconductor chips, like integrated circuits,ULSI, etc., liquid crystal devices, micro machines, thin-film magneticheads, and so forth. Here is taken a semiconductor device as an example.

FIG. 9 is a flow chart that shows a manufacturing process of asemiconductor device.

In step S21, the circuit of the semiconductor device is designed byusing CAD, for example.

In step S22, a mask with the designed circuit pattern is fabricated.Simultaneously, in step S23, a wafer is manufactured by using a materialsuch as silicon, for example.

In step S24, using the prepared exposure mask and wafer, the actualcircuit pattern is transferred and formed on the wafer by a lithographicprocess. The lithographic process includes the steps of, for example,pretreatment processing, coating of a resist, pre-baking, exposure,post-exposure baking (PEB), development/rinsing, post-baking, etching,ion implantation, removal of the resist, inspection, and so on.

In the next step S25, as a secondary step, the wafer fabricated in stepS24 is assembled into semiconductor chips. More specifically, assemblingsteps (dicing, bonding), packaging steps (steps of making chips), etc.are executed.

In the next step S26, the semiconductor device fabricated in step S25undergoes tests and repair like operation test, durability tests, and soforth.

Through these steps, the semiconductor device is completed and shipped.

According to the instant example of the manufacturing method, by usingan inexpensive exposure mask, the step of transfer and exposure can bemade inexpensive, and inexpensive semiconductor devices or opticaldevices can be supplied.

(Second Embodiment)

Next explained is the second embodiment of the invention.

FIGS. 10A through 10D are cross-sectional views that show the concept ofa process according to the second embodiment of the invention.

Here again, firstly, the nitride layer 1 is formed on the substrate 2 asshown in FIG. 10A.

Next as shown in FIG. 10B, the resist mask 3 of a predetermined patternis formed on the nitride layer 1. Usable as the material of the nitridelayer 1 is, for example, chromium nitride, gallium nitride, or the like.

Next as shown in FIG. 10C, hydrogen 4 and halogen element 4′ areimplanted. Then, in this step, hydrogen 4 and halogen elements 4′ areblocked by the mask 3, and they are selectively implanted into onlyportions of the nitride layer 1 through openings of the mask 3 to formhydrogen/halogen-implanted regions 1A.

Implantation of hydrogen 4 and halogen element 4′ can be obtained byirradiating their plasmas as will be explained later by way of anexample. At that time, incident angles of hydrogen 4 and halogen elemention beam to the substrate can be controlled by adjusting the plasmadensity, bias voltage, gas pressure, and others, and the patternconfiguration of the nitride layer 1 by this etching method can becontrolled. More specifically, if a pattern with rectangular shape isdesired, the rectangular shape can be obtained by lowering the plasmadensity, enhancing the bias voltage and thereby implanting ions normallyto the substrate.

The halogen used in this process may be fluorine, for example. Hydrogen4 and halogen elements 4′ may be implanted simultaneously, but need notbe implanted simultaneously, and may be implanted independently.

Next as shown in FIG. 1D, an excited oxygen-containing gas 5, such asoxygen plasma, is irradiated. As a result, the resist mask 3 is removed,and selective portions of the nitride layer 11, where hydrogen 4 andhalogen elements 4′ have been implanted, are etched and removed. Thereason why the nitride layer 1 is etched, possibly lies in highlyvolatile reactive products with a high equilibrium vapor pressure beinggenerated as a result of interaction of the nitride layer 1A containinghydrogen and halogen ions with oxygen.

In the step shown in FIG. 10C, upon implantation of hydrogen 4 andhalogen ions 4′, their penetration into the nitride layer 1 under theresist pattern of mask 3 is prevented because the resist mask 3 is madeof a light element. As a result, in the step shown in FIG. 10D, etchingof the nitride layer 1 by O₂ plasma is not occurred. Since hydrogen 4and halogen elements 4′ (in particular, fluorine) with small masses, inthe openings of resist pattern 3, they can intrude deeply into thenitride film 1.

According to the concentration profile of hydrogen 4 and halogenelements 4′ implanted into the nitride layer 1, the nitride layer 1 isetched by oxygen plasma processing 5 of FIG. 10D. Therefore,concentrations of hydrogen 4 and halogen elements 4′ change rapidly atpattern edges, and result in making a rectangular pattern.

Etching used in the invention occurs as a result of implantation effectsof hydrogen and halogen element, and the concentration profile ofimplanted elements, which is produced in the step of FIG. 10C, affectsthe pattern size and configuration, and even in the etching of FIG. 10Dusing oxygen gas. The micro-loading effect inherent to the existingetching methods is suppressed in this etching method.

As explained above, in the method according to the embodiment, themicro-loading effect, inherent to existing etching methods, issuppressed in the process of making a microstrucuture pattern of anitride film by etching, and enhancement of CD controllability ofpattern size can be expected.

Further, since the nitride film is etched by chemical etching withhighly volatile reactive products, the invention can cope with furtherreduction of the pattern size to a less than 50 nm.

Additionally, by adjusting the gas pressure, bias output, or the like,in the process of plasma irradiation of a gas containing hydrogen andhalogen elements, incident angles of hydrogen and halogen element ionsto the substrate can be controlled so as to control the patternconfiguration of the nitride film obtained.

Furthermore, upon repairing defects in photomasks and reticles using Crcompound films, or in various kinds of circuit boards having nitridefilm patterns, high-accuracy repairing is obtained without damagingportions other than the pattern defects.

At the same time, the invention enables fabricating exposure masks andvarious kinds of microstructure patterns easily and inexpensively.

The second embodiment will be explained below in greater detail withreference to the sixth to eighth examples.

(Sixth Example)

A microstructure pattern fabricating method of a CrN film and a TiN filmwill be explained below as the sixth example of the invention.

FIGS. 11A through 11F are cross-sectional views that roughly showcentral steps of making a CrN microstructure pattern used in thisexample.

In this example, two different processes A and B were executed.

As shown in FIG. 11A, in any of the processes A and B, a 100 nm thickCrN film 1 was deposited on a cleaned, 625 μm thick, 8-inch Si substrate2 by using a reactive sputtering apparatus, Cr as the target material,and using a nitrogen/argon mixed gas under the pressure of 5 mTorr.

Next as shown in FIG. 11B, in any of the processes A and B, a SiO₂ film6 and a resist mask 3 were formed. More specifically, first in asputtering apparatus, the 500 nm thick SiO₂ film 6 was deposited bychanging the target and the gas. After that, ZEP520 (Nippon Zeon),commercially available electron beam resist, was coated with a spincoater (not shown) at the spin velocity of 2000 rpm for 50 seconds.Then, through a baking process using a hot plate, a 350 nm thickphotosensitive film was formed, and a pattern was written by using anelectron beam writing apparatus of the acceleration voltage of 75 kV.For the purpose of obtaining a desired writing accuracy, multipleexposure method for forming a pattern by four-pass writing was employed,and optical proximity effect repair was executed by repairing the amountof irradiation. After the writing, through development, the resist mask3 was made.

Next as shown in FIG. 1C, plasma of hydrogen 4 and fluorine gas 4′ wasirradiated.

In case of the process A, plasma of CHF₃ gas (gas pressure: 0.6 Pa, flowrate: 100 sccm) was irradiated with the antenna output of 600 W and thebias output of 300 W for three minutes, using an inductively coupledplasma (ICP) source.

In contrast, in the process B, plasma of CHF₃ gas (gas pressure: 0.6 Pa,flow rate: 100 sccm) was irradiated with the antenna output of 750 W andthe bias output of 300 W for three minutes, using the ICP source.

As a result, as shown in FIG. 1D, selective portions of the SiO₂ film atthe openings of the resist mask 3 were etched by three-minute plasmaprocessing by CHF₃ gas to the surface of the CrN film 1, and the SiO₂film was patterned.

At that time, in the process A, hydrogen 4 and fluorine 4′ penetrateinto selective portions of the CrN film 1 at the opening of the resistmask 3, and implanted regions 1A are formed. Ions of hydrogen 4 andfluorine 4′ (in particular, hydrogen ions) with small masses intrudedeeply into the SiO₂ film 6 and the CrN film 1 under the openings of theresist mask, whereas the resist could prevent the ions of hydrogen 1 andfluorine 4′ from penetrating the SiO₂ film 6 and CrN film 1. This wasconfirmed by secondary ion mass spectrometry (SIMS).

On the other hand, in the process B, since the plasma density isincreased and the mean free path of ions is shorter than that of theprocess A, directions of ions tend to deviate from the normal line tothe substrate. As a result, as shown in FIG. 11D, hydrogen 4 andfluorine 4′ penetrate also into portions of the CrN film 1 under theresist mask 3, and make wider implanted regions 1A.

Next as shown in FIG. 11E, oxygen plasma (gas pressure: 0.7 Pa, flowrate: 100 sccm) 5 was irradiated with the antenna output of 500 W toremove the resist mask 3 and etches the implanted regions 1A under theopenings of the resist mask 3, thereby to obtain a pattern.

In the process A, even when the irradiation time of the oxygen plasma 5was elongated to 60 minutes, there was no change in pattern size andconfiguration of the CrN film 1 as shown in FIG. 11F. In contrast, inthe process B, a progress of side etching corresponding to the implantedregions of the CrN film 1 was confirmed as shown in FIG. 11F. This wasthe result of the directivity of ions during the CHF₃ gas plasmairradiation mentioned above.

Finally, by wet etching in a solution of ammonium fluoride, the SiO₂film 6 was removed, thereby to obtain a microstructure pattern (notshown) of the CrN film 1.

FIGS. 12A through 12D are enlarged diagrams of images of patternsobtained by the processes A and B, which were observed through ascanning electron microscope. FIG. 12A shows an enlarged image of anedge after irradiating oxygen plasma for 15 minutes in the process A,FIG. 12B shows that after irradiating oxygen plasma for five minutes inthe process B, FIG. 12C shows that after irradiating oxygen plasma for60 minutes in the process A, and FIG. 12D shows that after irradiatingoxygen plasma for 15 minutes in the process B.

It was confirmed from these enlarged images that all grooves, includingsuper fine pattern, could certainly be etched in the CrN film 1, in anyportions where oxygen ions could interact. That is, it was confirmedthat chemical etching with highly volatile reactive products occurred.

In case of the process A, side etching of the CrN film 1 was suppressed(FIG. 12C) even after oxygen plasma was irradiated for 60 minuteswhereas, in case of the process B, side etching of CrN film was occurredat the implanted region under the SiO₂ film 26 (FIG. 12D) by irradiationof oxygen plasma only for 15 minutes. This is because wide implantedregions 1A with hydrogen 4 and fluorine 4′ ions were made as explainedabove.

Next explained is a specific example in which a microstructure patternof TiN film was made using the instant example.

FIGS. 13A through 13D are cross-sectional views that roughly show mainsteps for making a TiN microstructure pattern used in this example.

As shown in FIG. 13A, the same deposited structure as that of the sixthexample was first formed. More specifically, a 100 nm thick TiN film 21was deposited on a cleaned, 625 μm thick, 8-inch Si substrate 2 by usinga reactive sputtering apparatus, Ti as the target material, and using anitrogen/argon mixed gas under the pressure of 5 mTorr. Additionally, a500 nm thick SiO₂ film 6 was deposited by changing the target and thegas.

Next as shown in FIG. 13B, a resist mask 3 was formed. Morespecifically, ZEP520 (Nippon Zeon), commercially available electron beamresist, was coated with a spin coater at the spin velocity of 2000 rpmfor 50 seconds. Then, through a baking process using a hot plate, a 350nm thick resist film was formed, and a pattern was written by using anelectron beam writing apparatus of the acceleration voltage of 75 kV.For the purpose of obtaining a desired writing accuracy, multipleexposure method for forming a pattern by four-pass writing was employed,and optical proximity effect repair was executed by repairing the amountof irradiation. After the writing, through development, the resist maskpattern 3 was formed.

After that, as shown in FIG. 13C, hydrogen 4 and fluorine 4′ wereimplanted. More specifically, in an ICP plasma etching apparatus, plasmaof CHF₃ gas (gas pressure: 0.6 Pa, flow rate: 100 sccm) was irradiatedwith the antenna output of 600 W and the bias output of 300 W for threeminutes. As a result, the SiO₂ film under the openings of the resistmask 3 were etched and implanted regions 21A with hydrogen 4 andfluorine 41 ions were formed in the underlying TiN film.

Next as shown in FIG. 13D, oxygen plasma was exposed. More specifically,oxygen plasma 5 (gas pressure: 0.7 Pa, flow rate: 100 sccm) wasirradiated with the antenna output of 500 W for 15 minutes. As a result,the resist mask 3 was removed and the implanted regions 21A of the TiNfilm under the opening of the mask 3 were patterned. Finally, the SiO₂film 6 was removed by wet etching in a solution of ammonium fluoride,thereby to obtain a microstructure pattern of the TiN film 21.

For the purpose of reviewing the effects of implantation of hydrogen andfluorine ions into CrN films and TiN films, the Inventor prepared thefollowing seven samples (A) through (G) were processed with oxygenplasma of the antenna output of 500 W (gas pressure: 0.7 Pa, flow rate:100 sccm), and compared etching rates CrN films, Cr films and TiN films.

A) CrN film prepared by irradiating plasma of CHF₃ gas of the antennaoutput of 750 W and the bias output of 300 W (gas pressure: 0.6 Pa, flowrate: 100 sccm) on the surface of CrN film for 30 seconds;

B) CrN film prepared by irradiating plasma of SF₆ gas of the antennaoutput of 750 W and the bias output of 300 W (gas pressure: 0.6 Pa, flowrate: 100 sccm) on the surface of CrN film for 30 seconds;

C) Cr film prepared by irradiating plasma of CHF₃ gas of the antennaoutput of 750 W and the bias output of 300 W (gas pressure: 0.6 Pa, flowrate: 100 sccm) on the surface of Cr film for 30 seconds;

D) CrN film prepared without plasma processing;

E) Cr film prepared without plasma processing;

F) TiN film prepared by irradiating CHF₃ gas plasma (gas pressure: 0.6Pa, flow rate: 100 sccm) with the antenna output of 750 W and the biasoutput of 300 W on the surface of the TiN film; and

G) TiN film without plasma processing.

Table 2 shows etching rates obtained when the samples A through G areexposed to oxygen plasma.

TABLE 2 Etching rate by oxygen plasma A) CrN (CHF₃-30s) 7.4 nm/min. B)CrN (SF₆-30s) 1.0 nm/min. C) Cr (CHF₃-30s) 0.3 nm/min. D) CrN (bulk) 1.1nm/min. E) Cr (bulk) 0.2 nm/min. F) TiN (CHF₃-30s) 0.3 nm/min. G) TiN(bulk) 0.08 nm/min. 

By comparing etching rates of samples A and B, the effect of hydrogenimplantation is confirmed. Further, by comparing etching rates ofsamples A and C, a difference is observed between the CrN film and theCr film, and effectiveness of hydrogen implantation to nitride films isappreciated. That is, the method according to the invention has beenconfirmed to enable selective etching in CrN films and Cr films.Additionally, from comparison between the etching rates of the samples(F) and (G), the method according to the invention can be appreciated tobe an etching method effective for nitrides containing an element otherthan Cr, as well.

In microstructure patterns of CrN films fabricated by the example shownabove, even after various kinds of plasma processing, no changes werefound in composition profile of constituent elements other than hydrogenand fluorine and in crystalline structure in the CrN film 1, and byX-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry(SIMS), X-ray diffraction (XRD) and transmission electron microscopy, itwas confirmed that damages by irradiation such as defects or dislocationwere not induced. That is, it was confirmed that no changes were broughtabout in optical property, electric property or mechanical property incompound layers used as photomasks.

FIGS. 14A through 14C are graphs that show results of XPS analysisobtained in the instant example. FIG. 14A shows XPS data of the CrN filmirradiated with CHF₃ gas plasma as a function of depth from surface,FIG. 14B shows XPS data of a non-processed CrN film prepared forcomparison; and FIG. 14C shows XPS data of the TiN film irradiated withCHF₃ gas plasma as a function of depth from surface.

It will be appreciated from these graphs that, through XPS analysis,peaks of NH_(x) indicating the binding of nitrogen and hydrogen wereobserved in the CrN film irradiated with CHF₃ gas plasma (FIG. 14A) andthe TiN film (FIG. 14C) in the binding energy spectrum of nitrogen 1sand that hydrogen ions play an important role in etching of nitridefilms.

As explained above, according to the instant example, it is appreciatedthat a microstructure pattern with a desired high accuracy can befabricated by dry etching using the hydrogen ion implantation effects ofthe nitride film. The microstructure pattern fabricating methodaccording to the embodiment was confirmed to exhibit the followingadvantages.

One of the advantages is suppression of micro-loading effects inherentto existing conventional etching methods, and therefore provides apossibility of enhancing CD controllability of pattern size. That is,the etching method according to the invention utilizes the effect of ionconcentration profile of hydrogen and fluorine implanted into thenitride film on the size and configuration of the subject to beprocessed. As a result, in a later oxygen etching process, etching ofthe nitride film is occurred in accordance with the concentrationprofile, and therefore, micro-loading effects inherent to existingconventional etching techniques are suppressed. Further, the nitridefilm is etched by chemical etching with highly volatile etching reactionproducts, and the method can be used for the fabrication ofmicrostructure as 50 nm or below.

The second advantage is to make it possible to control incident anglesof ions to the substrate by adjusting the plasma density, bias voltage,gas pressure, and/or other factors in the process of plasma irradiationof a gas containing hydrogen and fluorine, and thereby control thepattern configuration of the nitride film obtained. If a pattern with arectangular shape is desired, desirable conditions for implanting ionsnormally to the substrate can be obtained by lowering the gas pressure,elongating the mean free path of ions and increasing the bias voltage toenhance the straightness.

In case of photomasks for optical lithography, with reduced patternsize, it is necessary to make a much smaller opaque pattern like serifsand jogs for optical proximity repair or make a phase shift mask,particularly such as Levenson phase shift mask. Since the aspect ratioof the opaque pattern is high, it is difficult to control the size, theshape and the CD uniformity of patterns with a high accuracy when usingexisting conventional methods using wet etching or dry etching in themanufacturing process. However, by making a photomask by the etchingmethod according to the embodiment, it is possible to easily make amicrostructure pattern with high accuracy inexpensively and to fabricatea high-performance phase shift mask.

Although this example uses the CrN film and the TiN film as nitridefilms, it has been confirmed that the invention is similarly effectivealso when used with other compounds containing Cr and N, namely, CrCN,CrCON and TiAlN. Although these materials have been written as “CrN” and“TiN” in the foregoing explanation, composition ratio in each compoundis not limited to 1:1, but it will be need less to say that theinvention is similarly effective for nitride films having othercomposition ratios.

Furthermore, since the interaction of nitrogen in the nitride film withimplanted hydrogen and fluorine has a great contribution in thisexample, it will be appreciated that the invention is similarlyeffective also for other metallic nitrides, nitride semiconductors, andcompound materials containing nitrogen.

Additionally, the SiO₂ film 6 used in the instant example is notindispensable for making a pattern of a nitride film, but patterning ofa nitride film is possible also by making a resist mask directly on thenitride film.

Further, the SiO₂ film 6 used in the instant example is not limited toit, but it may be replaced with another film that penetrates asufficient amount of hydrogen ions and can be removed easily.

The example has been explained as using a sputtering apparatus fordeposition of films, but a CVD apparatus, for example, is also usable.

In the plasma processing employed in this example by using afluorine-containing gas, gases containing hydrogen and fluorine otherthan CHF₃, CF_(x)+H₂ and NH₃ indicated above are also usable. Theelement to be combined with hydrogen need not be fluorine and may be anyof other halogens. However, fluorine element with the smallest ionradius and mass will be the best.

Furthermore, although the instant example uses ICP as the plasma source,other usable apparatuses include RIE (reactive ion etching) apparatus,magnetron plasma apparatus, ECR-type RIE apparatus using electroncyclotron resonance, and plasma apparatus using a helicon plasma source.However, the ICP plasma source used in the instant example will be mostadvantageous in controllability of ion directivity because it has twosources, namely the source for generating plasma (plasma source) and thesource pulling ions from the plasma onto a sample (bias source), and canindependently control the density of the plasma and the bias potentialto the sample.

Additionally, in the etching process by oxygen plasma in the instantexample, the etching rate of the CrN film by oxygen plasma can becontrolled by changing the antenna output. Similarly, by changing theantenna output of the oxygen plasma, the etched patterns shape can bechanged as well.

Furthermore, in the etching process of the nitride film by oxygenplasma, if a bias output is also applied with antenna output, a metallicoxide film is formed on the surface of the nitride film, and etching ofthe nitride film by oxygen is largely restricted. Using this effect bybias application, it is possible to control the etching rate and patternconfiguration of the nitride film, make a pattern, and repair defects.

In the oxygen plasma processing, it is of course possible to control theetching rate and pattern configuration of the CrN film by further addinga gas like N₂, Cl₂, H₂, etc.

(Seventh Example)

Next explained is the seventh example of the invention, which is amethod of repairing defects in a photomask, reticle or any of variouskinds of circuit boards using a Cr compound film.

Explanation is first made about a method of repairing defects in aphotomask using Cr as the material of a opaque film. FIGS. 15A through15C are diagrams that show the concept of the defect repairing method ofa photomask according to the instant example.

First as shown in FIG. 15A, in a process of making a Cr pattern 8A,nitrogen ions were implanted into the Cr film by irradiating a nitrogenion beam of 60 keV onto a opaque defect 9A of a residue of the Cr filmby ion implantation, thereby to modify the opaque defect 9A to a CrNfilm.

Next as shown in FIG. 15B, plasma of a gas containing hydrogen 4 andfluorine 4′ was irradiated, thereby to form ion-implanted regions 10with hydrogen and fluorine in the substrate. This process was conductedin an ICP plasma etching apparatus by radiating plasma of CHF₃ gas (gaspressure: 0.6 Pa, flow rate: 100 sccm) under the antenna output of 600 Wand the bias output of 300 W.

After that, as shown in FIG. 15C, oxygen plasma 5 (gas pressure: 0.7 Pa,flow rate: 100 sccm) was exposed under the antenna output of 500 W. As aresult, the only portions of the CrN film, which is the opaque defect9A, was selectively etched, and the opaque defect was repaired.

Next explained is a method of repairing defects in a photomask using CrNas the material of a opaque film.

FIGS. 16A through 16C are diagrams that show the concept of the CrNphotomask defect repairing method according to the second embodiment ofthe invention.

First as shown in FIG. 16A, a hydrogen ion focused beam of 60 keV wasirradiated by ion implantation onto the opaque defect 9B of a residue ofa CrN film in the process of making a CrN pattern 8B to implant hydrogenions 4 by a high concentration into the film of the opaque defect.

Next as shown in FIG. 16B, fluorine ions were implanted into thesubstrate by plasma irradiation 4′ of a fluorine compound gas notcontaining hydrogen. In this process, plasma of SF₆ gas (gas pressure:0.5 Pa, flow rate 100 sccm) was irradiated under the antenna output of600 W and the bias output of 300 W for 30 seconds in an ICP plasmaetching apparatus.

Next as shown in FIG. 16C, oxygen plasma (gas pressure: 0.7 Pa, flowrate: 100 sccm) was irradiated under the antenna output of 500 W. As aresult, the only portion of the opaque defect 9B in the CrN film,implanted with hydrogen and fluorine, was selectively etched, and theopaque defect was repaired.

As explained above, it has been confirmed that the invention ensureshighly accurate repair without damaging when repairing defects ofphotomasks, reticles and various kinds of circuit boards using Crcompound films.

The instant example also utilizes the difference of oxygen etching ratebetween CrN films and Cr films, which are implanted with hydrogen andfluorine ions.

Also in case of repair of defects in the CrN film according to theinstant example, even after irradiation of various kinds of plasma ofgases containing hydrogen or oxygen gas no changes were found incomposition profile of constituent elements other than hydrogen andfluorine, in crystalline structure in the CrN film, and by x-rayphotoelectron spectroscopy (XPS), secondary ion mass spectrometry(SIMS), X-ray diffraction (XRD) and transmission electron microscopy. Itwas confirmed that damages by irradiation such as defects or dislocationwere not induced. That is, it was confirmed that no changes were broughtabout in optical property, electric property or mechanical property incompound layers used as masks.

FIG. 17 is a flow chart that shows a process of the defect repairingmethod according to the instant example. In this flow chart, the samesteps as those already explained with reference to FIG. 8 are labeledwith common reference numerals, and their detailed explanation isomitted here.

A difference of the flow chart of the instant example from FIG. 8 is toirradiate an ion beam of a halogen element in addition to the hydrogenion beam irradiation in step S4′. Fluorine is preferably used as thehalogen element. The hydrogen ion beam and the halogen element ion beammay be irradiated simultaneously. However, their irradiation need not beat the same time, but may be irradiated separately.

(Eighth Example)

Next explained is a specific example in which a microstructure patternof a GaN film was fabricated according to the second embodiment of theinvention.

FIGS. 18A through 18D are cross-sectional views that roughly illustratemain steps of the instant example.

First as shown in FIG. 18A, a multi-layered structure including a GaNfilm was formed. More specifically, a GaN film 31, approximately 1 μmthick, was deposited on a sapphire substrate 32 by MOCVD (metal-organicchemical vapor deposition) using TMG (trimethyl gallium) and NH₃ as mainsource material gases. Additionally, a 500 nm thick SiO₂ film 36 wasdeposited thereon by sputtering.

Next as shown in FIG. 18B, a resist mask pattern 3 was formed. Detailsof this step are the same as those already explained with reference toFIG. 13B.

Next as shown in FIG. 18C, hydrogen 4 and fluorine 4′ were implanted.More specifically, in an ICP plasma etching apparatus, plasma of CHF₃gas (gas pressure: 0.6 Pa, flow rate: 100 sccm) was irradiated with theantenna output of 600 W and the bias output of 300 W for five minutes.As a result, selective portions of the SiO₂ film under the openings ofthe resist mask 3 were etched and implanted regions 31A with hydrogen 4and fluorine 4′ ions were formed in the underlying GaN film.

Next as shown in FIG. 18D, oxygen plasma was irradiated. Morespecifically, oxygen plasma 5 (gas pressure: 0.7 Pa, flow rate: 100sccm) was irradiated with the antenna output of 500 W for 20 minutes. Asa result, the resist mask 3 was removed and the implanted regions 31A ofthe GaN film under the opening of the mask 3 were patterned. Finally,the SiO₂ film 6 was removed by wet etching in a hydrofluoric acid-basedsolution, thereby to obtain a microstructure pattern of the GaN film 31.

The GaN film 31, obtained, was formed into a desired pattern, and it hasbeen confirmed that the embodiment certainly makes it possible toreliably, easily realize patterning of gallium nitride compoundsemiconductors, which was not easy heretofore.

The pattern surface and side walls of the GaN film 31 after etching wereobserved through a scanning electron microscope. As a result, no etchpit was found and a smooth surface was confirmed. Further, compositionof the GaN surface after etching was measured by Auger electronspectroscopy. As a result, ratio of Ga and N did not change from thatprior to processing. This is probably because direct plasma irradiationonto the SiO₂ film 36 on the GaN film prevented the underlying GaN film31 from damage by plasma irradiation. That is, it has been confirmedthat the embodiment prevents degradation of the electric characteristicsand optical characteristics due to irradiation damage that wasinevitable in existing conventional plasma etching.

Although the invention has been explained, taking the GaN film as aspecific, the invention ensures the same effects also when applied toetching of InN, AlN, InGaN, AlGaN, and so on.

FIG. 19 is a diagram that shows the concept of a semiconductor devicethat can be manufactured by a method according to the invention. Thatis, FIG. 19 shows a cross-sectional configuration of a galliumnitride-based light emitting diode. Its general configuration isexplained below. That is, the light emitting element 100 has amulti-layered structure depositing semiconductors on a sapphiresubstrate 112. Deposited on the sapphire substrate are a buffer layer114, n-type contact layer 116, n-type cladding layer 118, light emittinglayer 120, p-type cladding layer 122 and p-type contact layer 124 inthis order.

Material of the buffer layer 114 may be n-type GaN, for example. Then-type contact layer 116 is an n-type semiconductor layer with a highcarrier concentration to ensure reliable ohmic contact with an n-sideelectrode 134. Its material may be GaN, for example. The n-type claddinglayer 118 and the p-type cladding layer 122 have the role of confiningcarriers in the light emitting layer 120, and are required to have widerenergy band gaps than the light emitting layer. Their material may beAlGaN having a wider band gap than the light emitting layer 120. Thelight emitting layer 120 is a semiconductor layer in which electriccharges implanted as a current in the light emitting element recombineand generate light. Its material may be undoped InGaN, for example. Thep-type contact layer 124 is a p-type semiconductor layer with a highcarrier concentration to ensure reliable ohmic contact with a p-sideelectrode. Its material may be GaN, for example.

On the p-type contact layer 124, a p-side electrode layer 126 isdeposited. On the n-type contact layer 118, an n-side electrode layer134 is deposited.

On a location of the p-type contact layer 124, a current blocking layer130 is formed. On the current blocking layer 130, a bonding pad 132 ofAu is deposited, and a part thereof is in contact with the p-sideelectrode 126. A wire, not shown, is bonded to the bonding pad 132 tosupply the element with a drive current.

The current blocking layer 130 has the role of preventing emission underthe Au electrode 32. That is, in the light emitting element 100, lightgenerated in the light emitting layer 120 is taken out upward throughthe electrode layer 126. However, because of a large thickness of theelectrode, the bonding pad 132 cannot transmit light. Therefore, byproviding the current block layer 130 not to implant the drive currentto under the bonding pad 132, useless emission is prevented.

Also on the n-side electrode 134, a bonding pad 132 is deposited. Thebonding pad 132 can be made by deposited Au film formation. Further, thesurface other than the bonding pad 132 is covered with a silicon oxidelayer 145.

The light emitting element 100 having the above-explained structure ismounted on a mount material such as lead frame, packaging substrate,etc., which are not shown, by bonding the bottom surface of thesubstrate 112 and bonding wires to the bonding pad, such that a drivecurrent is supplied.

For fabricating the light emitting diode explained above, it isnecessary to first make a wafer by sequentially depositing semiconductorlayers 114 through 124 on the substrate 112 and thereafter locallyexpose the n-type contact layer 116 by patterning the wafer in order tomake the n-side electrode 134. In this patterning process, the inventioncan be used. That is, it is possible to pattern the wafer made ofnitride semiconductors and locally expose the n-type contact layer 116by using the method already explained as the eighth example of theinvention.

According to the invention, in the patterning step, a predeterminedpatterning configuration can be made reliably, easily, without damagingsemiconductor layers.

The structure shown in FIG. 19 is not but an example among semiconductordevices that can obtained by the present invention. In addition to this,the invention can similarly make various other light emitting elementsusing nitride semiconductors, such as light emitting diodes andsemiconductor lasers, photodetective elements, optical modulators, orvarious kinds of electronic devices, such as transistors and diodes, andappropriate combinations thereof.

(Ninth Example)

Next explained is a specific example in which a multi-layered air-gapinterconnect structure (air-bridge wiring structure) in LSI having MOStransistors was fabricated as a ninth example of the invention.

FIGS. 20A through 20G are cross-sectional views that roughly illustratemain steps of the instant example.

First as shown in FIG. 20A, trench isolation regions 102 are formed on ap-type silicon substrate 101. Then, MOS transistors having source-drainregions 103, side-walls 104, gate oxide film 105, gate electrode 106 anda gate wiring 106 a are formed on the substrate 101.

Next as shown in FIG. 20B, a covering layer 107, a SiON layer 110 a(having a thickness of about 0.4 μm), lower SiO₂ layer 109 a (having athickness of about 0.05 μm) and an upper SiON layer 110 b (having athickness of about 0.4 μm). The SiON layer 110 a functions as atemporary layer for the formation of plug structure. The upper SiONlayer 110 b functions as a temporary layer for the formation of wiringlayer.

Next as shown in FIG. 20C, wirings 111 and plugs 112 are formed. Morespecifically, first, wiring grooves are formed in the upper SiON layer110 b by using the lower SiO₂ layer 109 a as an etching stopper layer.Then, contact holes which extend from the bottom of the wiring groove tothe source-drain region 103 through the lower SiO₂ layer 109 a and thelower SiON layer 110 a, are formed. An etching with fluoric gas isexecuted in order to make the contact holes, thus the fluorine isimplanted into the SiON layers 110 a and 110 b.

Alternatively, the contact holes may be formed before the formation ofthe wiring grooves.

Then, a barrier metal film 113 and a copper alloy film 114 are depositedby sputtering, and the wiring grooves and the contact holes are pluggedby the copper alloy by a re-flow process with an annealing at 400-500°C. Alternatively, the wiring grooves and the contact holes may beplugged by forming the copper alloy layer 114 by electroplating method.

Then, the remaining part of the barrier metal film 113 and the copperalloy film 114 which are left on the surface of the wafer withoutfilling the wiring grooves and the contact holes are removed bypolishing the surface of the wafer by CMP (chemical mechanicalpolishing) technique. As a result, the part of the barrier metal film113 and the copper alloy film 114 which remain in the wiring grooves inthe upper temporary SiON layer 110 b, function as the wiring of thefirst wiring layer 108.

Similarly, the part of the barrier metal film 113 and the copper alloyfilm 114 which remain in the contact holes in the lower temporary SiONlayer 110 a, function as the plugs 112. These plugs 112 verticallyconnect the wiring 111 of the first wiring layer 108 with thesource-drain region 103.

Next as shown in FIG. 20D, the similar structures are stacked. Morespecifically, the upper SiO₂ layer 109 a, the lower SiON layer 110 a,the SiO2 layer 109 a, the upper SiON layer 110 b are deposited. Then,the wiring grooves and the contact holes are formed. Then, the barriermetal film 113 and the copper alloy film 114 are deposited and there-flow process is executed. Then the CMP process is executed in orderto remove the extra part of the films 113 and 114. By repeating theabove-mentioned sequence specific times, the wirings 111 of the secondinterconnect layer 115 and the third interconnect layer 116, and theplugs 112 are formed. As the top layer, upper SiO2 layer 109 b whichfunctions as a protective layer is deposited.

Next as shown in FIG. 20E, openings 117 are formed in the upper SiO2layer 109 b covering the top of the stacked structure. The openings 117are formed so that the pad portions of the wirings 111 of the thirdinterconnect layer (top wiring layer) 116 is exposed.

Next as shown in FIG. 20F, hydrogen 118 is implanted. Following areexemplary depths from the surface of the SiON layers 110 a and 110 bwhich function as the temporary layers for the first through thirdinterconncect layers 108, 115 and 116 at this stage.

layer 110a layer 110b the first wiring layer 2.3-2.7 μm 1.85-2.25 μm thesecond wiring layer 1.4-1.8 μm 0.95-1.35 μm the third wiring layer0.50-0.90 μm 0.05-0.45 μm

In the step shown in FIG. 20F, the acceleration voltage for the hydrogenimplantation is controlled in accordance with these depths of the layers110 a and 110 b.

FIG. 21 is a graph showing the relationship between the accelerationvoltage of the hydrogen implantation and the depth of thehydrogen-implanted region.

The dose can be fixed at about 1×10¹⁴⁻¹⁵/cm² for the hydrogenimplantation. The acceleration voltage is controlled in the range of20-300 KeV so that the hydrogen-implanted regions are respectivelyformed in the each layers 110 a and 110 b in the each interconnectlayers 108, 115 and 116. By controlling the implantation condition inthis way, hydrogen would not reach the substrate 100.

The substrate 100 is mounted on the xyzθ-adjustable stage 120 and movedin a parallel direction to the surface of the mask 119. The alignmentand the gap spacing between the mask 119 and the substrate 100 areadjusted and hydrogen 118 is precisely implanted into the predeterminedposition. The pattern of the opening can be utilized as the marker forthe alignment. The positions of the mask 119 and the substrate 100 aredetected by using a laser beam. Thus, the mask 119 and the substrate 100are aligned and substrate 100 is moved to the predetermined position.

The gap spacing between the mask 119 and the substrate 100 can be alsocontrolled by the stage 120 and may be set at 50 μm.

By the above-explained procedure, the hydrogen-implanted regions arerespectively formed in the each layers 110 a and 110 b which function asthe temporary layers for the each interconnect layers 108, 115 and 116.

Then, the wafer is annealed at 200° C. for 15 minutes in a nitrogen orammonia gas atmosphere in order to recover the implantation-induceddamage.

Next as shown in FIG. 20G, the SiON layers 110 a and 110 b are removedby an oxygen plasma irradiation. Thus, the air-gap interconnectstructure is formed where each interconnect layers are separated by thelayers 109 a and 109 b.

This example also utilizes the phenomena that the etching rate of layerscontaining nitrogen with an oxygen plasma is remarkably increased byimplanting hydrogen into these layers. According to the invention, thenitrogen-containing layers between the barrier metal film 113 and thecopper alloy film 114 can be etched away and the air-gaps are formedtherebetween. As a result, each interconnect layers are separated by theair-gap layer 121. Since the dielectric constant of air is 1, parasiticcapacitance between each interconnect layers can be effectively reduced.

Conventionally, the process of such multilevel air-gap interconnectionswas fabricated by ashing process, which was required for eachinterconnect layer to remove temporary layer made by carbon. In contrastto this, according to the invention, the multilevel air-gapinterconnections structure can be formed at the same process by simplyirradiating the oxygen plasma. The process can be further simplified byutilizing appropriate masks for the implantation process of thehydrogen.

While the above-explained example include three-layeredinterconnections, the invention is not limited to the specific case. Itis apparent that the invention can be applied to the structures whichhave only two-layered interconnections or more than four-layeredinterconnections.

One of the features of the above-explained example is that the depths ofthe hydrogen implanted region are controlled by the implantationcondition such as acceleration voltage and the dose amount. According tothe invention, it is also easy to selectively form the air-gap only in aspecific interconnect layer within the multi-layered interconnectstructure by simply adjusting the implantation condition of hydrogen.

In the above-explained example, the lower and upper SiON layers 110 aand 110 b are employed as the temporary layer which can be etched awayby exposing to the excited oxygen atmosphere, and the SiO₂ layers 109 aand 109 b are employed as the permanent layers which is not etched away.However, the invention is not limited to this specific example. Anyother nitrogen-containing layers which can be selectively etched overthe SiO₂ layers 109 a and 109 b may be employed as the temporary layersas well.

One alternative may be SiOF layer doped with nitrogen. By using thislayer, barrier metal film 113 can be unused since SiOF doped withnitrogen prevent the diffusion of copper therein. Besides, this materialrealizes even higher etching rate when exposed to the oxygen plasmabecause nitrogen and fluorine are contained in the material.

As for the layers 109 a and 109 b, any other material which is notetched by the oxygen plasma, can be employed.

The lower SiO₂ layer 109 a may not be used. If the layer 109 a isunused, the lower temporary layer and its neighboring upper temporarylayer can be formed in a single temporary layer, and wiring grooves andcontact holes can be formed in this single temporary layer.

Embodiments of the invention have been explained heretofore by way ofspecific examples. However, the invention is not limited to thosespecific examples. For example, although such examples have beenexplained mainly about fabrication of photomasks, the invention is ofcourse applicable to semiconductor interconnect techniques and mask orpattern transfer techniques using X-rays or electron beams as exposuresources without being limited to photolithography.

Furthermore, also for various kinds of elements having compound layers,such as semiconductor devices and optical elements or micro machines,image display devices, and so on, the invention is similarly applicableand ensures the same effects.

While the present invention has been disclosed in terms of the preferredembodiment in order to facilitate better understanding thereof, itshould be appreciated that the invention can be embodied in various wayswithout departing from the principle of the invention. Therefore, theinvention should be understood to include all possible embodiments andmodification to the shown embodiments which can be embodied withoutdeparting from the principle of the invention as set forth in theappended claims.

The entire disclosure of Japanese Patent Applications No. 2000-095143filed on Mar. 30, 2000 and No. 2000-300633 filed on Sep. 29, 2000including specifications, claims, drawings and summaries areincorporated herein by reference in its entirety.

What is claimed is:
 1. A method of etching an object comprising:preparing the object containing nitrogen; introducing hydrogen into apredetermined region of the object; and selectively removing thepredetermined region from the object, by exposing the object to anatmosphere containing excited oxygen, wherein the object contains atleast one metal selected from the group consisting of chromium (Cr),titanium (Ti), aluminum (Al), molybdenum (Mo), tungsten (W), gallium(Ga), indium (In) and boron (B).
 2. The method according to claim 1,further comprising; side etching of the object from its side surfaceafter removing the predetermined region.
 3. The method according toclaim 1, wherein said introducing hydrogen also includes introducingfluorine into the predetermined region of the object.
 4. The methodaccording to claim 1, wherein said introducing hydrogen uses a mask toselectively implant hydrogen into the predetermined region in theobject.
 5. The method according to claim 1, wherein said introducinghydrogen is performed by ion implantation or laser doping, and saidselectively removing the predetermined region is performed byirradiation of plasma containing excited oxygen.
 6. The method accordingto claim 1, wherein the predetermined region is located in a certaindepth in the object and an amount of hydrogen introduced into thedetermined region is controlled by an implantation profile depending onthe depth.
 7. The method according to claim 6, wherein the predeterminedregion does not include a surface of the object.
 8. The method accordingto claim 7, wherein the object selectively contains nitrogen in thepredetermined region.
 9. A method of repairing a pattern comprising:making a portion of the pattern to be removed contain nitrogen andhydrogen; and etching the portion to be removed by exposing to anatmosphere containing excited oxygen, wherein the hydrogen isincorporated into the portion by ion implantation or laser doping, andthe atmosphere includes plasma containing excited oxygen.
 10. The methodaccording to claim 9, wherein the pattern is made of at least oneselected from the group consisting of metal, semiconductor and compound.11. The method according to claim 9, wherein the nitrogen isincorporated into the pattern prior to said making a portion of thepattern to be removed contain nitrogen and hydrogen.
 12. The methodaccording to claim 9, wherein fluorine is also incorporated into theportion during said making a portion of the pattern to be removedcontain nitrogen and hydrogen.
 13. The method according to claim 9,wherein the pattern contains at least one element selected from thegroup consisting of chromium (Cr), titanium (Ti), aluminum (Al),molybdenum (Mo), tungsten (W), gallium (Ga), indium (In) and boron (B).14. A method of manufacturing the semiconductor device having asubstrate, a plurality of transistor elements formed on the substrate,an interconnect layer formed over the transistor elements, a firstnitride layer below the interconnect layer having a first air portions,a second nitride layer on the interconnect layer having a second airportions, and a protective layer over the second nitride layer, themethod comprising: forming the first nitride layer without the first airportions and the second nitride layer without the second air portions;implanting hydrogen into corresponding portions of the nitride layers,the corresponding portions being the first and the second air portionsto be made; and irradiating plasma containing excited oxygen to thenitride layers to remove the corresponding portions thereby making thefirst and the second air portions in the nitride layers.